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Impedance Spectroscopy

(Or, how a sinusoidally varying voltage is used


to probe multiple electrical properties of materials)

Yun-Ju (Alex) Lee


June 13, 2002

Introduction
IS measures the resistance of a circuit to an applied voltage
Z(t) = E(t)/I(t), Z()=E()/I()
When E is applied as a sinusoidal function in a linear system, I
response can be represented by a sum of sinusoidal fuctions with
phase shifts.
If an equivalent circuit for the system being probed can be
constructed, then the resistance or capacitance values for each
circuit element can be backed out from Z.

Especially in electrochemical impendance


spectroscopy (EIS), the the voltage probe
signal is small (1-10mV) so the current
response is pseudolinear (side benefit: it
doesnt perturb the sample very much)

A Bard and L Faulkner, Electrochemical Methods: Fundamentals and Applications (2000)


http://www.gamry.com/G2/Appnotes/Reference/eistheory/theory/EIS_Theory.htm

Background Impedance and Circuit Elements


E(t) = E0cos(t), =2f
I(t) = I0 cos(t-)

E/I response for a resistor (=0)

Or, if one writes in complex notation:


E(t) = E0 exp(it)
I(t) = I0 exp(it - i)
Z(t) = Z0 exp(i) = Z0 (cos + isin )

E/I response for a capacitor (=-90)

E/I response for an inductor (=90)

http://www.gamry.com/G2/Appnotes/Reference/eistheory/theory/EIS_Theory.htm
http://www.bath.ac.uk/~chsacf/solartron/circp/html/acrci.htm

=-j Xc

= j Xl

For more complex circuits, use Kirchoffs rules

http://www.bath.ac.uk/~chsacf/solartron/circp/html/acrci.htm

Plotting Impedance
= 1/ = 1/RC

A Cole-Cole (or Nyquist) plot of the real and imaginary components of Z


for a circuit containing a capacitor and resistor in parallel (real world
example: a charged layer at an interface).

Named after KS Cole and RH Cole, J Chem Phys 9, 341 (1941)

Plotting Impedance

A Bode plot of a circuit containing a capacitor and resistor in parallel.


log |Z| and vs. log are plotted, showing explicitly the impact of
impedance.

http://www.gamry.com/G2/Appnotes/Reference/eistheory/theory/EIS_Theory.htm

Circuit Elements from Electrochemistry


1. Electrolyte resistance
R = l / A

l
A

WE, RE, CE
2. Double layer capacitance (~30F/cm for aqueous systems)
3. Polarization resistance
4. Charge transfer resistance
2

5. Coating capacitance
6. Constant phase element (a fudge factor)
7. Virtual inductor (adsorption?)
And

http://www.gamry.com/G2/Appnotes/Reference/eistheory/theory/EIS_Theory.htm

Diffusion (aka Warburg Impedance)


Warburg impedance = diffusion of chemical species to a large
planar electrode
Infinite diffusion layer thickness

Diffusion layer thickness

Also, in the Warburg region, = 45


http://www.consultrsr.com/resources/eis/diffusion.htm

Equivalent Circuit Model for Electrochemical Cells


Mixed Kinetic + Diffusion model

Cole-Cole plot

Bode plot
http://www.gamry.com/G2/Appnotes/Reference/eistheory/theory/EIS_Theory.htm

Some Applications of IS
Determine corrosion rates of materials*
Measure capacitance and resistance of SAMs to ascertain
thickness and packing quality
Probe linearity of electrical/electrochemical reactions
Characterize electrical activity across interfaces to determine
carrier concentration, etc.
Determine diffusion rate of counter ions in conducting
polymer/carbon nanotube composites

ASL Castela et al., Prog Org Coat 38, 1-7 (2000)


S Flink et al., Adv Mater 12, 1315-1327 (2000)
K Krischer et al., Angew Chem Int Ed 40, 850-869 (2001)
GZChen et al., Adv Mater 12, 522 (2000)

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